CN101294093A - Integrated preparation method for biological diesel oil and isolated plant - Google Patents
Integrated preparation method for biological diesel oil and isolated plant Download PDFInfo
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- CN101294093A CN101294093A CNA2007100520631A CN200710052063A CN101294093A CN 101294093 A CN101294093 A CN 101294093A CN A2007100520631 A CNA2007100520631 A CN A2007100520631A CN 200710052063 A CN200710052063 A CN 200710052063A CN 101294093 A CN101294093 A CN 101294093A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention belongs to the field of bio-diesel production and discloses an integrated production process and a device, wherein the process includes a step of constructing a continuous reaction system. The process comprises the following steps: (1) adding raw material oil and methanol into the reaction system including independent work units connected with each other through pipelines, pumps and valves, wherein each work unit is composed of a condensation segment, a reaction segment and a separation segment; (2) adding solid nanometer catalyst with a particle diameter of 25 to 50 nm in a reaction tower at an amount of 1 to 6% the weight of the raw material oil, and keeping the molar ratio of alcohol to oil at (6 to 48):1; (3) adding methanol 5 to 8 times the amount of the raw material oil, counter-contacting the methanol steam with the raw material oil, controlling the reaction temperature above the boiling point of methanol, and keeping the temperatures of a separation tower and the reaction tower at 65 to 95 DEG C and the reaction time of 2 to 10 h; (4) adding the catalyst at a height 2/3 the main body height of the reaction tower; (5) controlling the pressure in the reaction tower larger than about 25 to 45 mmHg; and (6) online separating glycerol to obtain the neutral bio-diesel. The invention also discloses a special device suitable for the integrated production process.
Description
Technical field
The invention belongs to technical field of biodiesel preparation, be specifically related to the integral process and the isolated plant thereof of biofuel.
Background technology
The production method of biofuel is chemical method basically both at home and abroad, and ubiquitous problem is: higher, the complex process of temperature of reaction; Use excessive methyl alcohol in the reaction process, subsequent technique must have corresponding pure retrieving arrangement, and treating processes is complicated, energy consumption is high; Water in the glyceride stock and free fatty acids can have a strong impact on the productive rate and the quality of biofuel; Purifying products complexity, esterification products are difficult to reclaim; The by product that reaction generates is difficult to remove, and uses acid base catalysator to produce a large amount of waste water, salkali waste (acid) liquid, and environment is caused secondary pollution.
Existing manufacturing technique generally adopts " intermittent type grease esterification technology ", and minority enterprise adopts " the continuous esterification technology of pressurizeing ".The shortcoming of intermittent type grease esterification technology is can not continuous production, and there is safety problem etc. in the process cost height; Free glycerol content is higher in the fatty acid methyl ester product that the continuous esterification technology of pressurizeing is produced, and is not suitable for use in biofuel, and 4%～5% salvage stores loss is arranged.The chemical catalyst of production biofuel, basic at present employing base catalysis, consumption is big, and aftertreatment is very complicated, the production cost height; Japan is being studied with enzymatic grease esterification technology at present, is to be higher than chemical catalyst far away but use the expense of enzyme catalyst, and this technology still is left to be desired at present, does not still possess the industrialization promotion condition.
By retrieval, patent documentation relevant such as Chinese invention patent prospectus (number of patent application: 200610126876.6) disclose " a kind of continous way prepares method of bio-diesel oil " with theme of the present invention, the core of this application is to use a loop turbulent flow reactor and 1-5 second reactor, stock oil wherein through pressurization, preheating, carries out esterification and transesterification reaction with methyl alcohol and compound alkaline-earth metal catalyst in the loop turbulent flow reactor.Enter second stage reaction after the first step reaction again and obtain finished product biofuel and byproduct glycerine thereof.The more traditional fixed reactors such as reactor of this patent application are innovations, but in view of turbulent flow reactor in this patent application (applicant oneself manufacturing) and the catalyzer (catalyzer of a kind of big class of buying from certain company, concrete that a kind of catalyzer that uses, do not have circumstantial letter in the specification sheets) be the core technology of invention, but in the specification sheets this is not had its ins and outs of full disclosure, the public is difficult to carry out this invention and reaches the alleged effect of this invention by the specification sheets introduction.At application number is 200610086175.4 (denominations of invention: the method for producing biological diesel oil through homogeneous successive reaction) in the document, provide a kind of it is said a kind of continuously, homogeneous phase prepares method of bio-diesel oil, natural fats and oils or abendoned oil and methyl alcohol or sodium hydroxide or potassium hydroxide and relevant solvent blend are formed homogeneous system carry out the preparation of biofuel, the core of invention it is said it is to finish in the pipeline reactor.Its defective is that specification sheets is that pipeline reactor is not done detailed explanation to the key device that carries out an invention, and does not also have accompanying drawing, and its ins and outs disclose insufficient, and those skilled in the art can't be implemented.China's utility model patent specification sheets (patent No.: 200620081061.6) disclose a kind of biofuel continuous production device, two second order reaction devices of this device are formed, its core component-reactor is a tubular reactor, be provided with equally distributed scale in the reactor, but this scale structure how, how to be installed in that specification sheets does not disclose more detailed information on the pipeline, also not have accompanying drawing to provide support, also belong to disclose insufficient.
As everyone knows, among the preparation technology and equipment of integral biological diesel oil, key is fully disclosing the refinement of support equipment (device), selection of catalysts and preparation and some important technical parameters, be the requisite important technology information of finishing invention and realizing the alleged technique effect of invention, and present in the existing document as yet not relevant for the enforceable information of integrated preparation biofuel, especially lack the key device of catalyzed reaction and the gordian technique and the condition of catalyzer and catalyzed reaction thereof.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, design a kind of integral process and isolated plant thereof of production biofuel, with solve in the prior art stock oil catalyzed reaction thoroughly and glycerine technical barrier such as can not onlinely remove.Integral manufacturing technique and the isolated plant that the present invention proposes has the raw material availability height, aftertreatment is simple, the discharging of no waste water, spent acid (alkali) liquid, characteristics such as non-environmental-pollution.
The present invention makes such realization:
A kind of integral manufacturing technique that is used for biofuel, its step comprises esterification and/or transesterification reaction, described reaction is finished in a successive reactive system, according to following steps:
(1) the animals and plants crude oil of high acid value or animals and plants Clean products and methyl alcohol are added in the described reactive system, this system independently constitutes a working cell by condensation segment, conversion zone and segregation section by each, connect and compose the entire reaction system by pipeline, pump and valve between the working cell, described condensation segment, conversion zone and segregation section are made of condenser, reaction tower and knockout tower respectively, described vegetable and animals oils adds from reaction tower top, and described methyl alcohol adds from knockout tower top;
(2) in the reaction tower of reactive system, pack into particle diameter be the nano-solid heteropoly acid of 25～50nm or/and heteropolybase catalyst, catalyst levels is 1%～6% of a vegetable and animals oils weight, keeping alcohol/molar equivalent is 6～48: 1;
(3) 5-8 by the vegetable and animals oils amount extraordinarily goes into methyl alcohol, makes methanol steam and vegetable and animals oils counter current contact, and control reaction temperature is more than the boiling point of methyl alcohol, and keeping the temperature of knockout tower and reaction tower is 65-95 ℃, and the reaction times is 2-10h;
(4) press 2/3 of reaction tower body height and add described catalyzer;
(5) control reaction tower internal pressure is higher than about normal atmosphere 25-45mmHg;
(6) ON-LINE SEPARATION goes out glycerine, makes the biofuel of preparation be neutral.
In the present invention, preferably, the mol ratio of the alcohol/oil of above-mentioned steps (2) is 9: 1.
In the present invention, preferably, the temperature of above-mentioned steps (5) is 75-85 ℃.
In the present invention, described heteropolyacid is selected from S
2O
8 2-/ ZrO
2-TiO
2, S
2O
8 2-/ γ-Al
2O
3-SiO
2Wherein a kind of or its combination.
In the present invention, described heteropolybase is selected from K
2CO
3/ γ-Al
2Wherein a kind of or its combination of O, KF/CaO, KF/CaO-MgO.
The isolated plant that is used for biofuel integral manufacturing technique of the present invention, have an esterification of finishing biofuel and/system of transesterification reaction, this system is by material tank (A), methanol tank (B), biofuel jar (C), glycerine storage tank (13-16) and 4 parallel working cells are formed, described working cell is by condensation segment independently, conversion zone and segregation section constitute, pass through pipeline between the working cell, pump and valve connect and compose the entire reaction system, described condensation segment, conversion zone and segregation section are respectively by condenser (1～4), reaction tower (5～8) and knockout tower (9～12) constitute, wherein, the condenser of each working cell, the vertical successively from top to bottom layout of reaction tower and knockout tower.
Described oil tank (A) is connected with reaction tower (5) with pipeline by valve (42); Described methanol tank (B) is connected with knockout tower (9) by valve (43); Lower part outlet end at knockout tower is connected with glycerine storage tank (13) with pipeline by valve (44), knockout tower (9) has a side outlet to be connected with the import of constant flow pump (22), the outlet of constant flow pump (22) is connected with reaction tower (6) in second working cell, until reaction tower (7) to the 3rd working cell, the reaction tower (8) of the 4th working cell connects, the outlet of knockout tower (9-12) bottom is connected with glycerine storage tank (13-16) by valve (44-47) respectively, and the side outlet of the knockout tower of the 4th working cell (12) is connected with biofuel storage tank (C) by constant flow pump (25).
In order to guarantee the placement of described catalyzer, the present invention's bottom part body level in reaction tower is equipped with a sieve plate, and its aperture is 1-2mm.
Technology of the present invention and device, it is parallel that to be divided into four working cells (preferentially be 3 working cells, as required can be) more than four working cells, each working cell is divided into condensation segment (condenser), conversion zone (reaction tower), three parts of segregation section (knockout tower) again, relates to 1 altogether and plant (or moving) thing oil tank, 1 methanol tank, 4 glycerine jars, 4 condensers, 4 reaction towers, 4 knockout towers, 4 constant flow pumps, 2 thermostatical circulating water pumps, 1 biofuel storage tank and some pipelines and valve.Described device can both have been bought from the market.Earlier methyl alcohol is added on the knockout tower (temperature 75-95 ℃) of first working cell, in knockout tower, form methanol vapor and enter reaction tower, will plant of the reaction tower upper end adding of (or moving) thing oil again from first working cell.Reaction tower is a jacketed type, internal layer is equipped with glass yarn and nano-solid heteropolybase catalyst (highly for reaction tower 2/3), skin is a thermal insulation layer, keep reaction tower temperature (75-95 ℃), plant (moving) thing oil from the top down with methyl alcohol reverse contact the in reaction tower from bottom to top, carry out transesterification reaction on the nano solid base catalyst surface.The biofuel that generates, glycerine and a small amount of unreacted methanol, the mixture of planting (moving) thing oil enter knockout tower together.Knockout tower also is a jacketed type, the mixture of internal layer for entering from reaction tower, glycerine and biofuel mutual solubility are little, in knockout tower, form the biliquid layer, because glycerine proportion is bigger, be in the lower floor of biliquid layer, upper strata biofuel raw product is extracted out from the knockout tower middle part by constant flow pump, and lower floor's glycerin layer flows into the glycerine storage tank from the knockout tower bottom.Skin is a thermal insulation layer, and keeping the knockout tower temperature is 75-95 ℃, and methyl alcohol constantly gasifies in the knockout tower, and methanol steam comes back to reaction tower and reacts.The raw product of biofuel is transported to (containing a small amount of unreacted planting (or moving) thing oil) conversion zone of second working cell by constant flow pump.(pressure-controlling in the reaction tower is than normal atmosphere about high 25-45mmHg according to the reaction tower internal pressure of second working cell, show by the pressure warning unit that is purchased), the an amount of methyl alcohol that replenishes, raw product with biofuel in the reaction tower (temperature is 75-95 ℃) of second working cell continues reaction, biofuel after reaction finishes, glycerine, the mixture of methyl alcohol etc. enters the knockout tower (temperature is 75-95 ℃) of second working cell, methyl alcohol is got back to reaction tower again with vapor form, glycerine deposits to the knockout tower bottom, open the knockout tower bottom valve, glycerine flows into storage tank; The raw product of biofuel is transported to the reaction tower of the 3rd working cell by constant flow pump.So repeatedly, up to the knockout tower of the 4th working cell separate be exactly esterification yield be biofuel product more than 96%.
In order further to optimize the present invention, the present invention has carried out experimental study to some important technical parameter among the preparation technology, and the result is as follows:
(1) the determining of temperature in the reactor
Technology of the present invention is employing methanol steam and rapeseed oil counter current contact, carries out transesterification reaction on the nano solid base catalyst surface, so the temperature of reaction should be more than the boiling point (65 ℃) of methyl alcohol, because reaction system is a multicomponent system, the boiling point of solution increases along with increasing of high boiling substance, by test of many times, the temperature of reaction system should maintain between 75 ℃-95 ℃.
(2) catalyzer and packed height thereof determines
Catalyzer and packed height thereof not only influence the speed of reaction, and affect the duration of contact of methanol steam and rapeseed oil, and the productive rate that rapeseed oil is converted into biofuel also has bigger influence.Test shows that the height of catalyzer and filler thereof is too low, and methanol steam and rapeseed oil are too short duration of contact, and the efficient of reaction is too low.If catalyzer and packed height thereof are too big, the resistance that methanol steam rises is too big, and segregation section liquid is easy to generate bumping, the reaction system instability.Usually catalyzer and packed height thereof are 2/3 of height for reactor, both can guarantee stable the carrying out that react, and can reach the ideal transformation efficiency.
(3) best molar ratio of methanol to oil determines
For the methanol steam that guarantees capacity fully contacts with rapeseed oil, therefore adopting the methyl alcohol and the mol ratio of oil when charging is 3: 1, with the 5-8 methanol steam doubly of oil mass, is entered by reactor bottom in addition, and adverse current contacts with rapeseed oil carries out transesterification reaction.In reaction, keep molar ratio of methanol to oil from start to finish about 10: 1, improve the transformation efficiency of rapeseed oil to greatest extent.
(4) the determining of pressure in the reactor
Pressure influence in the reactor the climbing speed and the life of catalyst of methanol steam.Pressure is too little, and the methanol steam climbing speed is too slow, and the dirty speed of rapeseed oil is too fast, and level of response is low, and rapeseed oil flows directly into segregation section.Pressure is excessive in the reactor, and the conversion zone boiling is violent, and the surface of damage catalyzer is too much at conversion zone accumulation reactant in the work-ing life of shortening catalyzer, and the very difficult segregation section that flows into of reactant, and reaction can not be carried out continuously.Test shows that the pressure in the reactor should be controlled at than about the high 25-45mmHg of normal atmosphere, and reaction effect is relatively good
The invention has the beneficial effects as follows:
(1) first characteristic of the present invention be the working cell of whole preparation facilities adopt vertical, be arranged in parallel, make whole production technology brief.
(2) second characteristics are that methanol vapor contacts with vegetable and animals oils is reverse, methyl alcohol enters from knockout tower top, in knockout tower, form steam and enter reaction tower from bottom to top, planting (moving) thing oil adds from top to bottom from reaction tower top, catalyst surface counter current contact in reaction tower is carried out transesterify or/and esterificationization should.
(3) the 3rd characteristics are ON-LINE SEPARATION of glycerine, and the work in-process of the biofuel of generation enter knockout tower, because glycerine and biofuel mutual solubility are little, form the biliquid layer in knockout tower.Glycerine proportion is bigger, is in the lower floor of biliquid layer, and the upper strata biofuel is discharged by knockout tower side exit end, and lower floor's glycerin layer then flows out from the knockout tower bottom, thereby has realized glycerine and biofuel ON-LINE SEPARATION.
(4) the nano-solid catalyzer of the present invention's preparation has active height, intensity is big, the life-span is long and be easy to the fixed characteristics.Patent publication No. is that the nanocatalyst of CN1858160A preparation need carry out centrifugation when being used to prepare biofuel, product and catalyst separating difficulty are big, the nano-solid catalyst strength of the present invention's preparation is big, be difficult for broken, the reaction tower bottom is equipped with sieve plate, liquid substance (as biofuel, glycerine etc.) can freely pass through, and solid matter (as the nano-solid catalyzer) is prevented from, and has realized that catalyzer separates automatically with product.
(5) the present invention prepares the biofuel transformation efficiency and reaches more than 98%, and technical target of the product meets U.S. ASTM D 6751-03 standard, need not do any processing and can directly supply with all kinds diesel engine fully and use.
Description of drawings
Biofuel integral process and device preparation signal thereof that Fig. 1 designs for the present invention.
Scheme the implication of Chinese and English numeral: A-and plant the implication that (moving) thing oil tank B-methanol tank C-biofuel storage tank Arabic numerals are represented:
1,2,3,4-condenser; 5,6,7,8-reaction tower; 9,10,11,12-knockout tower; 13,14,15,16-glycerine storage tank; 17-plants (moving) thing oil inlet; 18,19,20,21-methyl alcohol import; 22,23,24,25-constant flow pump;
26,27,28,29-valve; 30,32,34,36-catalyst inlet; 31,33,35,37-catalyst outlet; 38,39,40,41-measuring cell mouth.
The biofuel integral process signal that Fig. 2 designs for the present invention.
Fig. 3 is a nano-solid heteropoly acid catalyst S of the present invention
2O
8 2-/ TiO
2-ZrO
2Transmission electron microscope picture; Catalyzer (the S that shows the present invention's preparation
2O
8 2-/ TiO
2-ZrO
2) median size is about 30nm.
Fig. 4 is the nano-solid heteropolybase catalyst KF/CaO transmission electron microscope picture that the present invention prepares; Catalyzer (KF/CaO) median size that shows the present invention's preparation is about 25nm.
Fig. 5 is the nano-solid heteropolybase catalyst KF/CaO-MgO transmission electron microscope picture that the present invention prepares; Catalyzer (KF/CaO-MgO) median size that shows the present invention's preparation is about 50nm
Fig. 6 is the catalyzer KF/CaO-MgO access times that prepare of the present invention and the relation of esterification yield
Fig. 7 is the catalyzer KF/CaO-MgO regeneration access times that prepare of the present invention and the relation of esterification yield
Fig. 8 is that the different mol ratio of n (Ti) and n (Zr) is to catalyst S
2O
8 2-/ TiO
2-ZrO
2The influence of esterification yield
Fig. 9 is (NH
4)
2S
2O
8Concentration is to catalyst S
2O
8 2-/ TiO
2-ZrO
2The influence of esterification yield
Figure 10 is that the different dipping time of ammonium persulfate are to catalyst S
2O
8 2-/ TiO
2-ZrO
2The influence of esterification yield
Figure 11 is a catalyst S
2O
8 2-/ TiO
2-ZrO
2Maturing temperature to influence to the catalyzer esterification yield
Figure 12 is a catalyst S
2O
8 2-/ TiO
2-ZrO
2Roasting time to influence to the catalyzer esterification yield
Figure 13 is that n (Al) and n (Si) different mol ratio are to catalyst S
2O
8 2-/ γ-Al
2O
3-SiO
2The influence of esterification yield
Figure 14 is (NH
4)
2S
2O
8Concentration is to catalyst S
2O
8 2-/ γ-Al
2O
3-SiO
2The influence of esterification yield
Figure 15 is that the different dipping time of ammonium persulfate are to catalyst S
2O
8 2-/ γ-Al
2O
3-SiO
2The influence of esterification yield
Figure 16 is the S of catalyzer
2O
8 2-/ γ-Al
2O
3-SiO
2Maturing temperature to the influence of esterification yield
Figure 17 is the S of catalyzer
2O
8 2-/ γ-Al
2O
3-SiO
2Roasting time to the influence of esterification yield
Figure 18 is K
2CO
3With γ-Al
2O
3Amount of substance is to the influence of esterification yield
Figure 19 is catalyzer K
2CO
3/ γ-Al
2O
3Calcining temperature is to the influence of esterification yield
Figure 20 is catalyzer K
2CO
3/ γ-Al
2O
3Calcination time is to the influence of esterification yield
Figure 21 is the influence to esterification yield of CaO and MgO mass ratio
Figure 22 is the influence of the pickup of catalyzer KF/CaO-MgO to esterification yield
Figure 23 is the influence of the quality of catalyzer KF/CaO-MgO soaker water to esterification yield
Figure 24 is the influence of catalyzer KF/CaO-MgO dipping time to esterification yield
Figure 25 is the influence of the calcining temperature of catalyzer KF/CaO-MgO to esterification yield
Figure 26 is the influence of the calcination time of catalyzer KF/CaO-MgO to esterification yield
Figure 27 is the influence of the consumption of the KF among the catalyzer KF/CaO-MgO to esterification yield
Figure 28 is the influence of methanol usage to esterification yield
Figure 29 is the influence to esterification yield of esterification and transesterification reaction temperature
Figure 30 is the influence to esterification yield of esterification and transesterification reaction time
Embodiment
The device of embodiment 1 biofuel integral manufacturing technique for example
Technological line according to " summary of the invention ", the isolated plant of integrated preparation biofuel is by material tank (A), methanol tank (B), biofuel jar (C), glycerine storage tank (13-16) and 4 parallel working cells are formed, described working cell is by condensation segment independently, conversion zone and segregation section constitute, pass through pipeline between the working cell, pump and valve connect and compose the entire reaction system, described condensation segment, conversion zone and segregation section are respectively by condenser (1～4), reaction tower (5～8) and knockout tower (9～12) constitute, the condenser of each working cell, the vertical successively from top to bottom layout of reaction tower and knockout tower.Described material tank (A) is connected with reaction tower (5) with pipeline by valve (42); Described methanol tank (B) is connected with knockout tower (9) by valve (43); Lower part outlet end at knockout tower is connected with glycerine storage tank (13) with pipeline by valve (44), knockout tower (9) has a side outlet end to be connected with the entrance end of constant flow pump (22), the exit end of constant flow pump (22) links to each other with reaction tower (6) in second working cell, until reaction tower (7) to the 3rd working cell, the reaction tower (8) of the 4th working cell connects, the glycerine of knockout tower (9-12) links to each other with glycerine storage tank (13-16) by valve (44-47) respectively, and the side outlet end of the knockout tower of the 4th working cell (12) is connected with biofuel storage tank (C) by constant flow pump (25).
Material tank, methanol tank, biofuel jar, glycerine storage tank and condenser, reaction tower and knockout tower all can commercially be bought processed finished products in the present embodiment, do not have particular requirement on the technical parameter.The intravital bottom of reaction tower master of placing the nano-solid catalyzer is equipped with common sieve plate in a horizontal manner, and the aperture on the sieve plate is 1-2mm.Said apparatus and component thereof preferably adopt the stainless material manufacturing.Described under meter is from commercial purchase.Embodiment 2 nano-solid Preparation of catalysts
The nano-solid heteropoly acid catalyzer is selected from the following compounds preparation: ammonium persulfate/zirconium dioxide-titanium dioxide (S
2O
8 2-/ ZrO
2-TiO
2) or ammonium persulfate/γ-aluminium sesquioxide-silicon-dioxide (S
2O
8 2-/ γ-Al
2O
3-SiO
2) wherein a kind of or its combination.
Concrete preparation process:
(1) catalyst S
2O
8 2-/ ZrO
2-TiO
2Preparation: adopt chemical precipitation-high-temperature roasting method, its concrete preparation process is with reference to (golden auspicious sister-in-law .S
2O
8 2-/ ZrO
2-SiO
2Solid acid catalyst and catalysis synthesizing citric acid tri-n-butyl [J]. use chemical industry, 2005,34:32～35) method introduced carries out.Specifically: measure the 24ml titanium chloride, the 10ml zirconium oxychloride is soluble in water, makes precipitation agent with 25% ammoniacal liquor respectively, constantly stir, control titanium chloride and zirconyl chloride solution pH value be 8～10, static 2～6h.To generate titanium hydroxide and zirconium hydroxide thorough mixing then, and obtain A liquid, and with A liquid ageing 1～3h in 60～90 ℃ water-bath, filter, washing is to there not being chlorion (Cl
-) exist, with silver nitrate solution (AgNO
3) (the A liquid that takes a morsel is to wherein adding 1～2 AgNO in check
3If, there is not muddy phenomenon, show with no Cl
-).Dry by the fire 1～3h down at 110 ℃, with 0.1～2molL
-1Ammonium persulfate solution dipping 1～3h, suction filtration, drying, roasting 3～6h in 450～650 ℃ of muffle furnaces can make the nano-solid heteropoly acid catalyst S
2O
3 2-/ TiO
2-ZrO
2This catalyzer transmission electron microscope picture is seen Fig. 3, and the catalyzer median size of preparation is about 30nm.
(2) catalyst S
2O
8 2-/ γ-Al
2O
3-SiO
2Preparation: adopt sol-gel-high-temperature roasting method, its concrete preparation process with reference to (Cao Yuping, Li Yuguo, Sun Qinjun. the preparation of bitter earth nano powder and sign [J]. Shandong Normal University's journal, 2007,22:69～70).Make Al during for 3-6 in the pH value
3+, SiO
3 2-Hydrolysis and polycondensation form Al
3+-(OH)
n-Al
3+, Al
3+-(OH)
n-Si
4+, Si
4+-(OH)
n-Si
4+Colloidal sol naturally cools to room temperature, obtains γ-Al
2O
3-SiO
2Gel places the resistance furnace calcination with this gel, obtains γ-Al
2O
3-SiO
2Powder. use 0.1-2molL
-1(NH
4)
2S
2O
8Handle, contain oxo bridge and the polycentric composite nano solid heteropoly acid of cystine linkage catalyzer after 400-700 ℃ of roasting promptly gets.The catalyst particle size of preparation is about 30nm.
The preparation of nano-solid heteropolybase catalyst is selected from following compounds: potassium oxide/γ-aluminium sesquioxide (K
2O/ γ-Al
2O
3), wherein a kind of or its combination of Potassium monofluoride/calcium oxide (KF/CaO) or Potassium monofluoride/calcium oxide-magnesium oxide (KF/CaO-MgO).
Concrete preparation process:
(1) catalyst oxidation potassium/γ-aluminium sesquioxide (K
2O/ γ-Al
2O
3) preparation: adopt incipient impregnation-high-temperature calcination.Its concrete preparation process with reference to (Meng Xin .KF/CaO Soybean Oil by Transesterification prepares biofuel [J]. petrochemical complex, 2005,34:282～285) method introduced carries out.With pickling process with a certain amount of K
2CO
3Be carried on a certain amount of γ-Al
2O
3[m (K on the powder
2CO
3)/m (γ-Al
2O
3) be 0.1～0.6], water is cooked immersion solvent, deposits 1-3h after stirring, and in 110 ℃ of baking 1～5h, at 600 ℃ of calcining 4h, promptly gets the nano-solid heteropolybase catalyst.This catalyzer median size is about 40nm.
(2) preparation of catalyzer Potassium monofluoride/calcium oxide (KF/CaO): adopt incipient impregnation-high-temperature calcination.Its concrete preparation process with reference to (Meng Xin .KF/CaO Soybean Oil by Transesterification prepares biofuel [J]. petrochemical complex, 2005,34:282～285) method introduced carries out.The lime powder (particle diameter 20～40 orders) that takes by weighing certain mass 100g places beaker, stir in the KF solution of the finite concentration 0.1mol/L that adding prepares in advance, move in the chamber type electric resistance furnace after placing room temperature, calcine a few hours 4h down for 873 ℃ in certain temperature.Treat that it naturally cools to room temperature, kept dry promptly gets the nano-solid heteropolybase catalyst in the taking-up moisture eliminator.This catalyzer transmission electron microscope picture is seen Fig. 4, and the catalyzer median size that shows preparation is about 25nm.
(3) preparation of catalyzer Potassium monofluoride/calcium oxide-magnesium oxide (KF/CaO-MgO): adopt ball milling-hydro-thermal to synthesize-high-temperature calcination, its concrete preparation process is with reference to (Ma Hongxia, solid alkali MgO/Al
2O
3The performance of catalyzed oxidation mercaptan [J]. Nanjing University of Technology's journal, 2003,25:62～65) method introduced carries out.With 100g CaO, 20g MgO mixed grinding, the KF solution soaking 1～3h with 0.1mol/L stirs, and at 600 ℃ of calcining 5h, promptly gets the nano-solid heteropolybase catalyst.This catalyzer sem photograph is seen accompanying drawing 5, and the catalyzer median size of preparation is about 50nm.
The nano-solid catalyzer (KF/CaO-MgO) that its tower height 2/3 particle diameter of loading is 25nm in reaction tower main body (5,6,7,8), opening hot water pump makes the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 97.6%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
The nano-solid catalyzer (KF/CaO-MgO) that its tower height 2/3 particle diameter of loading is 35nm in reaction tower main body (5,6,7,8), opening hot water pump makes the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 98%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
The nano-solid catalyzer (KF/CaO-MgO) that its tower height 2/3 particle diameter of loading is 50nm in reaction tower main body (5,6,7,8), opening hot water pump makes the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 96%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
The nano-solid catalyzer (KF/CaO) that its tower height 2/3 particle diameter of loading is 40nm in reaction tower main body (5,6,7,8) is opened hot water pump and is made the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 97.6%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
Nano-solid catalyzer (the K that its tower height 2/3 particle diameter of loading is 30nm in reaction tower main body (5,6,7,8)
2CO
3/ γ-Al
2O), opening hot water pump makes the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 97.6%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
Nano-solid catalyzer (the S that its tower height 2/3 particle diameter of loading is 25nm in reaction tower main body (5,6,7,8)
2O
8 2-/ ZrO
2-TiO
2), open hot water pump and make the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 96%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
Embodiment 9 Application Examples (is raw material with the rapeseed oil)
Nano-solid catalyzer (the S that its tower height 2/3 particle diameter of loading is 45nm in reaction tower main body (5,6,7,8)
2O
8 2-/ ZrO
2-TiO
2), open hot water pump and make the temperature of production equipment reach the required temperature (85-95 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add rapeseed oil continuously, and the maintenance molar ratio of methanol to oil is 24-48: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 97%, and the key technical indexes of biofuel product meets U.S. ASTM D 6751-03 standard.
Nano-solid catalyzer (the S that its tower height 2/3 particle diameter of loading is 45nm in reaction tower main body (5,6,7,8)
2O
8 2-/ γ-Al
2O
3-SiO
2), open hot water pump and make the temperature of production equipment reach the required temperature (75-85 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add Oleum Gossypii semen oil continuously, and the maintenance molar ratio of methanol to oil is 12-36: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 96.9%, and makes the biofuel of preparation be neutral.
Embodiment 11 Application Examples (is raw material with the Oleum Gossypii semen)
Nano-solid catalyzer (the S that its tower height 2/3 particle diameter of loading is 25nm in reaction tower main body (5,6,7,8)
2O
8 2-/ γ-Al
2O
3-SiO
2), open hot water pump and make the temperature of production equipment reach the required temperature (75-85 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the plant oil tank, by the flow of under meter controlling plant oil in knockout tower (9), in reaction tower, add Oleum Gossypii semen oil continuously, and the maintenance molar ratio of methanol to oil is 12-36: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 97.5%, and makes the biofuel of preparation be neutral.
Nano-solid catalyzer (the S that its tower height 2/3 particle diameter of loading is 50nm in reaction tower main body (5,6,7,8)
2O
8 2-/ ZrO
2-TiO
2), open hot water pump and make the temperature of production equipment reach the required temperature (65-80 ℃) of production, open cold condenser (1,2,3,4).Open methanol tank valve (26) and add 2 liters of methyl alcohol, when the methanol vapor that wait methyl alcohol forms enters reaction tower (5), open the lard jar in knockout tower (9), by the flow of under meter control lard, in reaction tower, add lard continuously, and the maintenance molar ratio of methanol to oil is 6-24: 1.React after 30 minutes, open methanol tank valve (27) and add 1.5 liters of methyl alcohol, wait for and open constant flow pump (22) when methanol vapor that methyl alcohol forms enters reaction tower (6) knockout tower (10) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 13 automatically) of knockout tower (9) is transported to reaction tower (6) continuation reacts.Open methanol tank valve (28) after 30 minutes and add 1 liter of methyl alcohol, wait for and open constant flow pump (23) when methanol vapor that methyl alcohol forms enters reaction tower (7) knockout tower (11) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 14 automatically) of knockout tower (10) is transported to reaction tower (7) continuation reacts.Open methanol tank valve (29) after 30 minutes and add 0.5 liter of methyl alcohol, wait for and open constant flow pump (24) when methanol vapor that methyl alcohol forms enters reaction tower (8) knockout tower (12) in, the biofuel raw product (glycerine is separated to knockout tower lower tank 15 automatically) of knockout tower (11) is transported to reaction tower (8) continuation reacts.Open constant flow pump (25) after 30 minutes, the biofuel (glycerine is separated to knockout tower lower tank 16 automatically) of knockout tower (12) is transported to biofuel storage tank (C).The biofuel esterification yield is more than 95.7%.Cetane value: 52.0; Zero pour :-2 ℃; Ash content: 0.002%; Flash-point:＞100 ℃; 20 ℃ of kinematic viscosity υ: 6.6mm
2/ s; Acidity: 3.65mgKOH/100ml.
Embodiment 13: Application Example (with Chinese tallow tree seed crude oil is raw material, optimizes the experiment of catalyst technology parameter)
Nano-solid heteropoly acid catalyzer (S
2O
8 2-/ ZrO
2-TiO
2) preparation: the preparation raw material is TiCl
4, ZrOCl
2, NH
3H
2O, (NH
4)
2S
2O
8, preparation process is with reference to (Dong Guochen, nano solid supper corrosive acid SO
4 2-/ TiO
2-SiO
2[J]. Northeast Normal University newspaper natural science edition, 2004,36:27～31) method introduced carries out.
Under laboratory condition, studied catalyzer prepares biofuel to Chinese tallow tree seed crude oil correlation technique parameter.The nano-solid heteropoly acid catalyst S of using in the present embodiment
2O
8 2-/ ZrO
2-TiO
2Prepare according to the method shown in the embodiment 2.Get catalyst S
2O
8 2-/ ZrO
2-TiO
22.6g, Chinese tallow tree seed crude oil 100mL (acid number is 87mg/g NaOH), commercially available methanol 36mL, 70 ℃ of temperature of reaction, reaction times 3h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) different Ti: Zr is to the influence of catalyst activity
Get 10g ZrO
2And TiO
2Composite oxides, use 0.6molL
-1(NH
4)
2S
2O
8Solution impregnation 3h, 600 ℃ of maturing temperatures, roasting 4h, investigate different n (Ti): n (Zr) sees Fig. 8 to the influence of catalyst activity.As seen from Figure 8, n (Ti): n (Zr) is very big to the activity of such catalysts influence, and n (Ti): n (Zr) is that 6～7 o'clock catalytic activitys are higher.
(2) (NH
4)
2S
2O
8The concentration of solution is to the influence of catalyst activity
N (Ti): n (Zr) is 7,600 ℃ of maturing temperatures, roasting 4h, dipping time are 3h, investigates (the NH of different concns
4)
2S
2O
8To the influence of catalyst activity, the condition of preparation biofuel is the same, and Fig. 9 is seen in its influence.As seen from Figure 9, ammonium persulphate concentration has very big influence to catalytic activity, and its concentration is too high or too low all unfavorable to catalytic activity, and the ammonium persulfate solution optimum concn is 0.6molL
-1The time catalytic activity the best.
(3) the ammonium persulphate dipping time is to the influence of catalyst activity
N (Ti): n (Zr) is 7,600 ℃ of maturing temperatures, roasting 4h, ammonium persulfate solution concentration are 0.6molL
-1, investigate of the influence of different dipping time to catalyst activity, the condition of preparation biofuel is the same, and Figure 10 is seen in its influence.As seen from Figure 10, different dipping time catalyst activities have certain influence, catalytic activity the best when dipping 3h.
(4) maturing temperature is to the influence of catalyst activity
N (Ti): n (Zr) is 7, (NH
4)
2S
2O
8Concentration is 0.6molL
-1, dipping time is 3h, roasting 4h, investigates the influence of different maturing temperatures to catalyst activity, the condition of preparation biofuel is the same, Figure 11 is seen in its influence.As seen from Figure 11, the influence that maturing temperature is bigger to catalytic activity, optimum calcination temperature is 600 ℃.
(5) roasting time is to the influence of catalyst activity
N (Ti): n (Zr) is 7, (NH
4)
2S
2O
8Concentration is 0.6molL
-1, dipping time is that 3h, maturing temperature are 600 ℃, investigates the influence of different roasting time to catalyst activity, the condition of preparation biofuel is the same, Figure 12 is seen in its influence.As seen from Figure 12, the influence that roasting time is bigger to catalytic activity, best roasting time is 4h.
Embodiment 14: Application Example (with lard is raw material, optimizes the experiment of catalyst technology parameter).
Under laboratory condition, studied catalyzer prepares biofuel to lard correlation technique parameter.The nano-solid heteropoly acid catalyst S of using in the present embodiment
2O
8 2-/ γ-Al
2O
3-SiO
2Prepare according to the method shown in the embodiment 2.Get catalyst S
2O
8 2-/ γ-Al
2O
3-SiO
23.0g, lard 100mL (acid number is 105mg/g NaOH), commercially available methanol 36mL, 80 ℃ of temperature of reaction, reaction times 5h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) influence of different al, Si comparison catalyst activity
To different al, Si than mixture gel 1molL
-1Concentration (NH
4)
2S
2O
8Dipping, dipping time 2h at 550 ℃ of roasting 4h, investigates activity of such catalysts with the method for preparing biofuel and sees Figure 13.As seen from Figure 13, n (Al): n (Si) is 6 o'clock, and catalyst activity is the highest.
(2) different (NH
4)
2S
2O
8Dipping concentration is to the influence of catalyst activity
N (Al): n (Si) is 6,550 ℃ of maturing temperatures, roasting 4h, dipping time are 2h, investigates (the NH of different concns
4)
2S
2O
8To the influence of catalyst activity, the condition of preparation biofuel is the same, and Figure 14 is seen in its influence.As seen from Figure 14, ammonium persulphate concentration has very big influence to catalytic activity, and its concentration is too high or too low all unfavorable to catalytic activity, and the ammonium persulfate solution optimum concn is 1.0molL
-1The time catalytic activity the best.
(3) the ammonium persulphate dipping time is to the influence of catalyst activity
N (Al): n (Si) is 6,550 ℃ of maturing temperatures, roasting 4h, (NH
4)
2S
2O
8Concentration is 1molL
-1, investigate of the influence of dipping different time to catalyst activity, the condition of preparation biofuel is the same, and Figure 15 is seen in its influence.As seen from Figure 15, different dipping time have certain influence to catalyst activity, catalytic activity the best when dipping 1.5h.
(4) maturing temperature influences to catalyst activity that n (Al): n (Si) is 6, roasting 4h, (NH
4)
2S
2O
8Concentration is 1molL
-1Dipping time is 2h, investigates the influence of different maturing temperatures to catalyst activity, and the condition of preparation biofuel is the same, and Figure 16 is seen in its influence.As seen from Figure 16, the influence that maturing temperature is bigger to catalytic activity, optimum calcination temperature is 550 ℃.
(5) roasting time is to the influence of catalyst activity
N (Al): n (Si) is 6, (NH
4)
2S
2O
8Concentration is 1molL
-1Dipping time is 2h, and maturing temperature is 600 ℃, investigates the influence of different roasting time to catalyst activity, and the condition of preparation biofuel is the same, and Figure 17 is seen in its influence.As seen from Figure 17, the influence that roasting time is bigger to catalytic activity, best roasting time is 4.5h.
Embodiment 15: Application Example (with concise rapeseed oil is raw material, optimizes the experiment of catalyst technology parameter).
Under laboratory condition, studied catalyzer prepares biofuel to rapeseed oil correlation technique parameter.The nano-solid heteropoly acid catalyzer K that uses in the present embodiment
2CO
3/ γ-Al
2O
3, prepare according to the method shown in the embodiment 2.Get catalyzer K
2CO
3/ γ-Al
2O
33.5g, concise rapeseed oil 100mL (acid number is 1.5mg/gNaOH), commercially available methanol 36mL, 75 ℃ of temperature of reaction, reaction times 2h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) catalyst proportion is to the influence of catalytic performance
As seen from Figure 18: 1. work as K
2CO
3/ γ-Al
2O
3Proportioning is lower than at 50% o'clock, along with K
2CO
3The increase gradually of ratio, esterification yield increases gradually, illustrates that the catalytic efficiency of catalyzer is more and more higher, and this is because work as K
2CO
3/ γ-Al
2O
3Proportioning is lower than at 50% o'clock, the K of carrier surface
2CO
3It is more even to distribute, and eclipsing effect is little, along with K
2CO
3The increase gradually of ratio, K
2CO
3The quantity of the basic center that produces after the thermolysis also increases gradually, thereby makes K
2CO
3/ γ-Al
2O
3Alkalescence strengthen gradually, and then catalytic efficiency also improves thereupon; 2. work as K
2CO
3/ γ-Al
2O
3Proportioning is higher than at 50% o'clock, along with K
2CO
3The increase gradually of composition, esterification yield reduces gradually, illustrates that the catalytic efficiency of catalyzer is more and more lower, and this is because work as K
2CO
3/ γ-Al
2O
3Proportioning is higher than at 50% o'clock, the K of carrier surface
2CO
3What distribute is inhomogeneous, and eclipsing effect is big, along with K
2CO
3The increase gradually of ratio, K
2CO
3The basic center that produces after the thermolysis is also overlapping gradually, does not only make K
2CO
3/ γ-Al
2O
3Alkalescence strengthen and to make its reduction on the contrary, and then catalytic efficiency also decreases.
(2) change of calcining temperature is to the test of catalyst efficient
As seen from Figure 19: 1. when calcining temperature was lower than 600 ℃, along with the rising of calcining temperature, esterification yield improved gradually, illustrated that the catalytic efficiency of catalyzer is more and more higher, and this is because when calcining temperature is lower than 600 ℃, along with the rising of calcining temperature, K
2CO
3Rate of decomposition also improve gradually, thereby the quantity of the basic center that is produced is also more and more, the alkalescence of catalyzer is also more and more stronger, catalytic efficiency also improves naturally thereupon.2. when calcining temperature is higher than 600 ℃, rising along with calcining temperature, the variation of esterification yield is also not obvious, the catalytic efficiency that catalyzer is described changes not quite, and this is because temperature is too high, can form bigger gathering, produce sintering phenomenon, reduce specific surface, thereby the calcining temperature quantity that also can not make basic center that raises again increases, catalytic efficiency during with 600 ℃ the incinerating catalyzer compare and change and not obvious.
(3) change of calcination time is to the influence of catalyst efficient
As seen from Figure 20: 1. when calcination time is lower than 4h, along with the prolongation of calcination time, esterification yield improves gradually, and promptly the catalytic efficiency of catalyzer is along with the prolongation of calcination time promotes rapidly, this is because when calcination time is lower than 4h, along with the prolongation K of calcination time
2CO
3Rate of decomposition also improve gradually, thereby the quantity of the basic center that is produced is also more and more, the alkalescence of catalyzer is also more and more stronger, catalytic efficiency also improves naturally thereupon.
2. when calcination time during greater than 4h, along with the prolongation of calcination time, esterification yield changes little, and promptly the catalytic efficiency of catalyzer changes along with the prolongation of calcination time and be not obvious, and this is because when calcination time during greater than 4h, along with the prolongation K of calcination time
2CO
3Rate of decomposition again can't improve, thereby calcination time prolongs the quantity that also can not make basic center again and increases, its catalytic efficiency during with 4h the incinerating catalyzer compare and change and not obvious.
Embodiment 16: Application Example (with concise rapeseed oil is raw material, optimizes the experiment of catalyst technology parameter).
Under laboratory condition, studied catalyzer prepares biofuel to rapeseed oil correlation technique parameter.The nano-solid heteropoly acid catalyzer KF/CaO that uses in the present embodiment prepares according to the method shown in the embodiment 2.Get catalyzer KF/CaO3.0g, concise rapeseed oil 100mL (acid number is 1.5mg/gNaOH), commercially available methanol 36mL, 75 ℃ of temperature of reaction, reaction times 2h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) Preparation of catalysts test
According to principle of orthogonal test, determine the concrete scheme of orthogonal test, as following table.
Table 1 factor level
Table 2 Preparation of Catalyst orthogonal experiments
By R value in the table 2 as can be seen, the principal element that influences the biofuel transformation efficiency is KF and CaO mass ratio, and each factor influences size order and is: A＞B＞D＞C, and by K
iBe worth as can be known, the optimization processing condition that the catalysis rapeseed oil prepares the nano-solid heteropolybase catalyst KF/CaO preparation of biofuel are A
2B
3D
3C
3
The stability test of catalyst optimization processing condition:
According to optimizing 5 groups of catalyzer of the parallel preparation of processing condition and preparing biofuel with rapeseed oil under the same conditions, with the gas Chromatographic Determination esterification yield, the results are shown in following table 3 under the same terms.
The catalyzer (KF/CaO) of table 3 the present invention preparation is optimized the stable process conditions test
Table 3 data declaration, the result of test is in the error allowed band, and the catalytic performance of this catalyzer has stability preferably.
Embodiment 17: Application Example (with the soybean oil is raw material, optimizes the experiment of catalyst technology parameter).
Under laboratory condition, studied the correlation technique parameter of catalyzer to Study on Preparation of Biodiesel from Soybean oil.The nano-solid heteropoly acid catalyzer KF/CaO-MgO that uses in the present embodiment prepares according to the method shown in the embodiment 2.Get catalyzer KF/CaO-MgO3.0g, soybean oil 100mL (acid number is 1.5mg/gNaOH), commercially available methanol 36mL, 80 ℃ of temperature of reaction, reaction times 2h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) CaO and MgO mass ratio are to the influence of catalytic activity
Take by weighing well-mixed CaO of 100g and MgO, add the aqueous solution 150mL that contains 25gKF, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, be the feedstock production biofuel with the soybean oil, investigate CaO and MgO mass ratio Figure 21 is seen in the influence of catalytic activity.As shown in Figure 21, m (CaO)/m (MgO) is 5 o'clock, and catalytic activity is the highest.
(2) relation of the pickup of KF and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5, the aqueous solution 150mL that adds the KF of 10-35g, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates the pickup of KF Figure 22 is seen in the influence of catalytic activity.As shown in Figure 22, the pickup of KF is 25% o'clock of CaO/MgO quality, and catalytic activity is the highest.
(3) relation of the quality of soaker water and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5, add 25g KF and 100-150g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates the quality of soaker water Figure 23 is seen in the influence of catalytic activity.As shown in Figure 23, the quality of soaker water is 130% o'clock of CaO/MgO quality, and catalytic activity is the highest.
(4) relation of dipping time and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5, add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and the immersion certain hour, at 600 ℃ of calcining 5h, with the soybean oil is the feedstock production biofuel, investigates dipping time Figure 24 is seen in the influence of catalytic activity.As shown in Figure 24, dipping time is 1h, and catalytic activity is the highest.
(5) relation of calcining temperature and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5, add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 400-900 ℃ of temperature lower calcination 5h, with the soybean oil is the feedstock production biofuel, investigates calcining temperature Figure 25 is seen in the influence of catalytic activity.As shown in Figure 25, during 600 ℃ of calcining temperatures, catalytic activity is the highest.
(6) relation of calcination time and catalytic activity
Take by weighing well-mixed CaO of 100g and MgO[m (CaO)/m (MgO)=5, add 25g KF and 130g water, add a small amount of bubble flower alkali and ammoniacal liquor, fully stir and immersion 1h, at 600 ℃ of calcining certain hours, with the soybean oil is the feedstock production biofuel, investigates calcination time Figure 26 is seen in the influence of catalytic activity.As shown in Figure 26, calcination time is 5h, and catalytic activity is the highest.
Embodiment 18 Application Examples (with the abendoned oil is raw material, optimizes the experiment of catalyst technology parameter).
Under laboratory condition, studied catalyzer prepares biofuel to abendoned oil correlation technique parameter.The nano-solid heteropoly acid catalyst S of using in the present embodiment
2O
8 2-/ ZrO
2-TiO
2Prepare according to the method shown in the embodiment 2 with KF/CaO-MgO.Get catalyst S
2O
8 2-/ ZrO
2-TiO
2With each 3.00g of KF/CaO-MgO, abendoned oil 100mL (acid number is 100mg/gNaOH), commercially available methanol 36mL, 90 ℃ of temperature of reaction, reaction times 8h, esterification yield adopts gas chromatograph for determination (model: PE-500, fid detector, 2010 chromatographic working stations).
(1) catalyst levels is to the influence of esterification yield
By above-mentioned reaction conditions, keep other factors constant, change catalyst levels and investigate its influence esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T 5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and two stage esterification yields and catalyst levels relation are seen Figure 27.Know by Figure 27, Esterification Stage, the nano-solid heteropoly acid consumption reaches specified acid number during for 3.5g, this moment the esterification yield maximum, in the transesterify stage, nano-solid heteropolybase consumption is a 2.8g ester interchange conversion rate maximum.
(2) methanol usage is to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, keep other factors constant, change methanol usage and investigate its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, and acid number is pressed GB/T 5530-1998 and measured, reach below the 1mgKOH/g, carry out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 28.Know that by Figure 28 when methanol usage was 48mL during acid catalysis, when methanol usage was 36mL during base catalysis, it is maximum that esterification yield reaches, suitable when taking all factors into consideration the disposable add-on of methyl alcohol and being 48mL.
(3) esterification and transesterification reaction temperature are to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, methanol usage 48mL keeps other factors constant, changes temperature of reaction and investigates its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T 5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 29.Known that by Figure 29 temperature of reaction is at 65～70 ℃ during base catalysis, temperature of reaction is at 70 ℃ during acid catalysis, and it is maximum that esterification yield reaches, and takes all factors into consideration, and temperature of reaction is set in 70 ℃ during acid catalysis, and temperature of reaction is set in 68 ℃ during base catalysis.
(4) esterification and transesterification reaction time are to the influence of esterification yield
By above-mentioned reaction conditions, the nano-solid heteropoly acid consumption is that 3.5g, nano-solid heteropolybase consumption are 2.8g, methanol usage 48mL keeps other factors constant, changes the reaction times and investigates its influence to esterification yield, the esterification yield of Esterification Stage characterizes by measuring acid number, acid number is pressed GB/T 5530-1998 and is measured, and reaches below the 1mgKOH/g, carries out the reaction in transesterify stage, esterification yield is with gas chromatography determination, and the esterification yield in two stages and catalyst levels relation are seen Figure 30.As shown in Figure 30, the base catalysis the reaction time is 3h, and temperature of reaction is 3.5h during acid catalysis, and it is maximum that esterification yield reaches.
Nano-solid catalyzer of the present invention can use 16～82 its activity to remain unchanged substantially continuously, can also regenerate, and activity and live catalyst after the regeneration are suitable.Fig. 3 and Fig. 4 have shown that catalyzer KF/CaO-MgO is to rapeseed oil production biofuel result of use.
Fig. 6 has shown the catalyzer KF/CaO-MgO access times of the present invention's preparation and the relation of esterification yield, and Fig. 7 has then shown the relation of catalyzer KF/CaO-MgO regeneration access times of the present invention and esterification yield
From Fig. 6 and Fig. 7 as can be seen, nano-solid heteropolybase catalyst KF/CaO-MgO uses continuously and the back of regenerating uses its catalytic performance fluctuation less, substantially do not influence catalytic effect, with patent publication No. be that CN1858160A relatively has more superior catalytic performance, and the relation of the access times of CN1858160A and undeclared catalyzer, regeneration access times and esterification yield.
Claims (8)
1, a kind of integral manufacturing technique that is used for biofuel, its step comprises esterification and/or transesterification reaction, described reaction is finished in a successive reactive system, it is characterized in that, according to following steps:
(1) the animals and plants crude oil of high acid value or animals and plants Clean products and methyl alcohol are added in the described reactive system, this system independently constitutes a working cell by condensation segment, conversion zone and segregation section by each, connect and compose the entire reaction system by pipeline, pump and valve between the working cell, described condensation segment, conversion zone and segregation section are made of condenser, reaction tower and knockout tower respectively, described vegetable and animals oils adds from reaction tower top, and described methyl alcohol adds from knockout tower top;
(2) in the reaction tower of reactive system, pack into particle diameter be the nano-solid heteropoly acid of 25～50nm or/and heteropolybase catalyst, catalyst levels is 1%～6% of a vegetable and animals oils weight, keeping alcohol/molar equivalent is 6～48: 1;
(3) 5-8 by the vegetable and animals oils amount extraordinarily goes into methyl alcohol, makes methanol steam and vegetable and animals oils counter current contact, and control reaction temperature is more than the boiling point of methyl alcohol, and keeping the temperature of knockout tower and reaction tower is 65-95 ℃, and the reaction times is 2-10h;
(4) press 2/3 of reaction tower body height and add described catalyzer;
(5) control reaction tower internal pressure is higher than about normal atmosphere 25-45mmHg;
(6) ON-LINE SEPARATION goes out glycerine, makes the biofuel of preparation be neutral.
2, technology according to claim 1, wherein alcohol/the molar equivalent of step (2) is 9: 1.
3, technology according to claim 1, wherein the temperature of step (3) is 75-85 ℃.
4, technology according to claim 1 is characterized in that described heteropolyacid is selected from S
2O
8 2-/ ZrO
2-TiO
2, S
2O
8 2-/ γ-Al
2O
3-SiO
2Wherein a kind of or its combination.
5, technology according to claim 1 is characterized in that described heteropolybase selects white K
2CO
3/ γ-Al
2Wherein a kind of or its combination of O, KF/CaO, KF/CaO-MgO.
6, the isolated plant that is used for the described biofuel integral manufacturing technique of claim 1, it is characterized in that, have an esterification of finishing biofuel and/system of transesterification reaction, this system is by material tank (A), methanol tank (B), biofuel jar (C), glycerine storage tank (13-16) and 4 parallel working cells are formed, described working cell is by condensation segment independently, conversion zone and segregation section constitute, pass through pipeline between the working cell, pump and valve connect and compose the entire reaction system, described condensation segment, conversion zone and segregation section are respectively by condenser (1～4), reaction tower (5～8) and knockout tower (9～12) constitute, described condenser, the vertical successively from top to bottom layout of reaction tower and knockout tower.
7, device according to claim 6 is characterized in that, described oil tank (A) is connected with reaction tower (5) with pipeline by valve (42); Described methanol tank (B) is connected with knockout tower (9) by valve (43); Lower part outlet end at knockout tower is connected with glycerine storage tank (13) with pipeline by valve (44), knockout tower (9) has a side outlet to be connected with the import of constant flow pump (22), the outlet of constant flow pump (22) is connected with reaction tower (6) in second working cell, until reaction tower (7) to the 3rd working cell, the reaction tower (8) of the 4th working cell connects, the outlet of knockout tower (9-12) bottom is connected with glycerine storage tank (13-16) by valve (44-47) respectively, and the side outlet of the knockout tower of the 4th working cell (12) is connected with biofuel storage tank (C) by constant flow pump (25).
8, according to claim 6 or 7 described devices, it is characterized in that the bottom part body level is equipped with a sieve plate in described reaction tower, its aperture is 1-2mm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260595A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Process for producing fatty acid methyl ester with grease waste |
| CN101691526B (en) * | 2009-09-30 | 2012-11-28 | 华中农业大学 | Method for preparing biodiesel by using biological carapace solid base catalyst |
| CN103060097A (en) * | 2012-12-30 | 2013-04-24 | 上海油好同盟新能源科技有限公司 | Continuous production line for producing biodiesel under catalysis of solid catalyst |
| CN105754718A (en) * | 2016-04-26 | 2016-07-13 | 上海应用技术学院 | Method for preparing biodiesel |
| CN106588958A (en) * | 2015-10-14 | 2017-04-26 | 上虞新和成生物化工有限公司 | Production system and method for continuously preparing alkynol di-Grignard reagent |
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| CN1317357C (en) * | 2005-01-27 | 2007-05-23 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
| CN100503786C (en) * | 2006-06-02 | 2009-06-24 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
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| CN101691526B (en) * | 2009-09-30 | 2012-11-28 | 华中农业大学 | Method for preparing biodiesel by using biological carapace solid base catalyst |
| CN102260595A (en) * | 2010-05-26 | 2011-11-30 | 北京石油化工学院 | Process for producing fatty acid methyl ester with grease waste |
| CN103060097A (en) * | 2012-12-30 | 2013-04-24 | 上海油好同盟新能源科技有限公司 | Continuous production line for producing biodiesel under catalysis of solid catalyst |
| CN103060097B (en) * | 2012-12-30 | 2014-11-26 | 上海油好同盟新能源科技有限公司 | Continuous production line for producing biodiesel under catalysis of solid catalyst |
| CN106588958A (en) * | 2015-10-14 | 2017-04-26 | 上虞新和成生物化工有限公司 | Production system and method for continuously preparing alkynol di-Grignard reagent |
| CN106588958B (en) * | 2015-10-14 | 2018-09-28 | 上虞新和成生物化工有限公司 | A kind of continuous production system and method for preparing alkynol di Grignard reagent |
| CN105754718A (en) * | 2016-04-26 | 2016-07-13 | 上海应用技术学院 | Method for preparing biodiesel |
| CN106753813A (en) * | 2017-01-19 | 2017-05-31 | 中国科学院广州能源研究所 | A kind of solid acid catalysis waste oil continuous esterification deacidification couples the continuous recycling device of methyl alcohol |
| CN106753813B (en) * | 2017-01-19 | 2020-09-04 | 中国科学院广州能源研究所 | Solid acid catalysis waste oil continuous esterification deacidification coupling methanol continuous recycling device |
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